TW202237555A - Polycarbonate resin, method for producing same, and optical lens - Google Patents

Abstract

The present invention provides a polycarbonate resin having a high refractive index, low Abbe number, and high moist heat resistance. The above problem, according to one embodiment, can be solved by a polycarbonate resin including structural units represented by general formula (1).

Description

Monomer composition and manufacturing method of polycarbonate resin

The present invention relates to polycarbonate resin and its production method. Moreover, this invention also relates to the optical lens containing polycarbonate resin.

Optical glass or optical resin is used as the material of the optical lens used in the optical system of various cameras such as cameras, film-integrated cameras, and video cameras. Although optical glass is excellent in heat resistance, transparency, dimensional stability, and chemical resistance, it has problems of high material cost, poor formability, and low productivity.

On the other hand, optical lenses made of optical resins have the advantage of being mass-produced by injection molding. For example, polycarbonate resin and the like are used in lenses for cameras. However, in recent years, the development of resins with high refractive index is required due to the reduction in weight, thickness and size of products. Generally speaking, when the refractive index of the optical material is high, the lens unit with the same refractive index can be realized by a surface with a smaller curvature, so the amount of aberration generated on the surface can be reduced. As a result, the number of lenses can be reduced, the decentering sensitivity of the lens can be reduced, and the thickness and weight of the lens can be reduced.

Also, in general, in the optical system of a camera, aberration correction is performed by combining a plurality of concave lenses and convex lenses. That is, chromatic aberration is eliminated synthetically by combining a concave lens having a chromatic aberration of the opposite sign to that of a convex lens for chromatic aberration generated by a convex lens. At this time, the concave lens system requires high dispersion (that is, low Abbe number).

Therefore, development of a resin suitable for an optical lens having a high refractive index and a low Abbe's number is being carried out. For example, Patent Document 1 discloses that a copolymer of a bisphenol A-type polycarbonate structural unit and a structural unit represented by the following formula (E) increases the refractive index. In the examples of Patent Document 1, it is described that the refractive index is 1.62-1.64 and the Abbe number is 23-26. Such an increase in the refractive index is considered to be due to the constituent unit represented by the formula (E).

In addition, Patent Document 2 discloses a copolymer of polycarbonate resin and bisphenol A including a structural unit having a terpene structure. In the examples of this document, it is described that the refractive index is 1.616 to 1.636. Furthermore, the constituent units disclosed in this document are different from formula (E).

As described above, polycarbonate resins and optical lenses having a high refractive index and a low Abbe number have not yet been provided.

Furthermore, in recent years, water resistance and heat resistance have been required for various electronic devices. As an environmental test to evaluate the water resistance and heat resistance of such electronic equipment, "PCT test" (pressure cooker test) is carried out. The test is a heat and humidity resistance test, which is accelerated in time to evaluate the intrusion of moisture into the interior of the sample. Therefore, optical lenses made of optical resins used in electronic equipment are required not only to have high refractive index and low Abbe number, but also to maintain optical properties after PCT test. [Prior Art Literature] [Patent Document]

[Patent Document 1] International Publication No. 2007/142149 [Patent Document 2] Japanese Patent Application Laid-Open No. 6-25398

[Problem to be Solved by the Invention]

The problem to be solved by the present invention is to provide polycarbonate resin with high refractive index, low Abbe number and high heat and humidity resistance. In addition, it is also an object to provide an excellent optical lens by using the resin. [Means to solve the problem]

(通式(1)中，X表示碳數1～4之伸烷基，a及b各自獨立地表示1～10之整數)。 [2]如[1]之聚碳酸酯樹脂，其進一步包含下述通式(2)及/或下述通式(3)表示之構成單位；

(通式(2)中，Y表示碳數1～4之伸烷基，c及d各自獨立地表示1～10之整數)；

(通式(3)中， Z表示碳數1～4之伸烷基， R ₁～R ₆係各自獨立地表示氫原子、碳數1～20之烷基、碳數1～20之烷氧基、碳數5～20之環烷基、碳數5～20之環烷氧基、碳數6～20之芳基或碳數6～20之芳氧基， e及f各自獨立地表示0～5之整數)。 [3]如[2]之聚碳酸酯樹脂，其係包含通式(1)～(3)表示之構成單位的聚碳酸酯樹脂，其中 通式(1)表示之構成單位的比例為10～80莫耳%， 通式(2)表示之構成單位的比例為10～60莫耳%， 通式(3)表示之構成單位的比例為5～80莫耳%。 [4]如[2]之聚碳酸酯樹脂，其係包含通式(1)～(3)表示之構成單位的聚碳酸酯樹脂，其中 通式(1)表示之構成單位的比例為20～80莫耳%， 通式(2)表示之構成單位的比例為10～60莫耳%， 通式(3)表示之構成單位的比例為5～70莫耳%。 [5]如[2]之聚碳酸酯樹脂，其係包含通式(1)及(2)表示之構成單位的聚碳酸酯樹脂，其中 通式(1)表示之構成單位的比例為10～80莫耳%， 通式(2)表示之構成單位的比例為20～90莫耳%。 [6]如[2]之聚碳酸酯樹脂，其係包含通式(1)及(2)表示之構成單位的聚碳酸酯樹脂，其中 通式(1)表示之構成單位的比例為30～60莫耳%， 通式(2)表示之構成單位的比例為40～70莫耳%。 [7]一種光學透鏡，其包含如[1]～[6]中任一項之聚碳酸酯樹脂。 [8]一種方法，其係如[1]～[6]中任一項之聚碳酸酯樹脂之製造方法，該方法包含 使包含下述通式(4)表示之二羥基化合物的二羥基化合物、與碳酸二酯進行熔融聚縮合的步驟；

(通式(4)中，X表示碳數1～4之伸烷基，a及b各自獨立地表示1～10之整數)。 [發明之效果] As a result of repeated studies to solve the above-mentioned problems, the inventors of the present invention found that the above-mentioned problems can be solved by the following polycarbonate resin and optical lens, and completed the present invention. The present invention is, for example, as described below. [1] A polycarbonate resin comprising a constituent unit represented by the following general formula (1);

(In the general formula (1), X represents an alkylene group having 1 to 4 carbon atoms, and a and b each independently represent an integer of 1 to 10). [2] The polycarbonate resin according to [1], further comprising a constituent unit represented by the following general formula (2) and/or the following general formula (3);

(In the general formula (2), Y represents an alkylene group with 1 to 4 carbon atoms, and c and d each independently represent an integer of 1 to 10);

(In general formula (3), Z represents an alkylene group with 1 to 4 carbons, and R ₁ to R ₆ each independently represent a hydrogen atom, an alkyl group with 1 to 20 carbons, and an alkoxy group with 1 to 20 carbons radical, cycloalkyl with 5 to 20 carbons, cycloalkoxy with 5 to 20 carbons, aryl with 6 to 20 carbons or aryloxy with 6 to 20 carbons, e and f each independently represent 0 ~ an integer of 5). [3] The polycarbonate resin as in [2], which is a polycarbonate resin comprising constituent units represented by general formulas (1) to (3), wherein the proportion of constituent units represented by general formula (1) is 10 to 80 mol%, the ratio of the constituent unit represented by the general formula (2) is 10-60 mole%, and the ratio of the constituent unit represented by the general formula (3) is 5-80 mole%. [4] The polycarbonate resin as in [2], which is a polycarbonate resin comprising constituent units represented by general formulas (1) to (3), wherein the ratio of constituent units represented by general formula (1) is 20 to 80 mol%, the ratio of the constituent unit represented by the general formula (2) is 10-60 mole%, and the ratio of the constituent unit represented by the general formula (3) is 5-70 mole%. [5] The polycarbonate resin as in [2], which is a polycarbonate resin comprising the constituent units represented by the general formulas (1) and (2), wherein the ratio of the constituent units represented by the general formula (1) is 10 to 80 mol%, and the proportion of the constituent unit represented by the general formula (2) is 20 to 90 mol%. [6] The polycarbonate resin according to [2], which is a polycarbonate resin comprising the constituent units represented by the general formulas (1) and (2), wherein the ratio of the constituent units represented by the general formula (1) is 30 to 60 mol%, and the ratio of the constituent unit represented by the general formula (2) is 40 to 70 mol%. [7] An optical lens comprising the polycarbonate resin according to any one of [1] to [6]. [8] A method for producing the polycarbonate resin according to any one of [1] to [6], the method comprising making a dihydroxy compound including a dihydroxy compound represented by the following general formula (4) 1. Carrying out the step of melt polycondensation with carbonic acid diester;

(In the general formula (4), X represents an alkylene group having 1 to 4 carbon atoms, and a and b each independently represent an integer of 1 to 10). [Effect of Invention]

The polycarbonate resin of the present invention exhibits high refractive index, low Abbe's number and high resistance to heat and humidity. Also, by using resin, an excellent optical lens can be obtained.

(通式(1)中，X表示碳數1～4之伸烷基，a及b各自獨立地表示1～10之整數)。 The present invention will be described in detail below. (1) Polycarbonate resin The polycarbonate resin of this invention is a polycarbonate resin which has a structural unit represented by General formula (1) (it is also called "a structural unit (1)" hereafter).

(In the general formula (1), X represents an alkylene group having 1 to 4 carbon atoms, and a and b each independently represent an integer of 1 to 10).

The polycarbonate resin of the present invention may contain one or more other structural units in addition to the structural unit (1). The other constituent units are preferably terpene derivative units or binaphthol derivative units.

(通式(2)中，Y表示碳數1～4之伸烷基，c及d各自獨立地表示1～10之整數)。

(通式(3)中， Z表示碳數1～4之伸烷基， R ₁～R ₆係各自獨立地表示氫原子、碳數1～20之烷基、碳數1～20之烷氧基、碳數5～20之環烷基、碳數5～20之環烷氧基、碳數6～20之芳基或碳數6～20之芳氧基， e及f各自獨立地表示0～5之整數)。 Specifically, the polycarbonate resin of the present invention preferably further includes a binaphthol derivative unit represented by the following general formula (2) and/or a terpene derivative unit represented by the following general formula (3).

(In the general formula (2), Y represents an alkylene group having 1 to 4 carbon atoms, and c and d each independently represent an integer of 1 to 10).

(In general formula (3), Z represents an alkylene group with 1 to 4 carbons, and R ₁ to R ₆ each independently represent a hydrogen atom, an alkyl group with 1 to 20 carbons, and an alkoxy group with 1 to 20 carbons radical, cycloalkyl with 5 to 20 carbons, cycloalkoxy with 5 to 20 carbons, aryl with 6 to 20 carbons or aryloxy with 6 to 20 carbons, e and f each independently represent 0 ~ an integer of 5).

The polycarbonate resin of the present invention preferably contains the structural units represented by the general formulas (1) to (3), more preferably consists of the structural units represented by the general formulas (1) to (3). "Consisting essentially of" in this specification means that the polycarbonate resin of the present invention may contain other constituent units within the range that does not impair the effect of the invention. For example, among the constituent units of the polycarbonate resin of the present invention, preferably at least 90%, more preferably at least 95%, and more preferably at least 98% are constituent units represented by general formulas (1) to (3) constituted. When the polycarbonate resin of the present invention contains constituent units represented by general formulas (1) to (3), it is preferable that the proportion of constituent units represented by general formula (1) is 10 to 80 mol%, and that of general formula (2) The ratio of the constituent unit represented is 10 to 60 mol%, and the ratio of the constituent unit represented by the general formula (3) is 5 to 80 mol%. Also, from the viewpoint of obtaining a higher refractive index, it is more preferable that the ratio of the constituent unit represented by the general formula (1) is 20 to 80 mol%, and the ratio of the constituent unit represented by the general formula (2) is 10 to 60 mol%. %, the ratio of the constituent unit represented by the general formula (3) is 5 to 70 mol%. The polycarbonate resin of the present invention having a composition with a better ratio has a very high refractive index of 1.670 or higher which has not been achieved so far.

The polycarbonate resin of the present invention preferably contains the structural units represented by the general formulas (1) and (2), more preferably consists of the structural units represented by the general formulas (1) and (2). For example, among the constituent units of the polycarbonate resin of the present invention, preferably at least 90%, more preferably at least 95%, and more preferably at least 98% are constituent units represented by general formulas (1) and (2) constituted. When the polycarbonate resin of the present invention contains the constituent units represented by the general formula (1) and (2), it is preferable that the proportion of the constituent units represented by the general formula (1) is 10 to 80 mol%, and the general formula (2) The ratio of the constituent units represented is 20 to 90 mole%. By setting it as such a ratio, the polycarbonate resin which has the very high refractive index of 1.670 or more which has not achieved hitherto can be obtained. Also, from the viewpoint of obtaining better formability, it is more preferable that the ratio of the constituent unit represented by the general formula (1) is 30 to 60 mole %, and the ratio of the constituent unit represented by the general formula (2) is 40 to 70 mole %. Ear%.

When the polycarbonate resin of the present invention contains structural units represented by general formulas (1) to (3), or contains structural units represented by general formulas (1) and (2), in what form are these structural units contained? There is no special limitation in the resin. In one aspect of the present invention, the polycarbonate resin may contain a copolymer containing structural units represented by general formulas (1) to (3) or structural units represented by general formulas (1) and (2), or may contain Ternary resin or binary resin that is a homopolymer composed of respective constituent units. Alternatively, it may be a blend of a copolymer containing constituent units represented by general formulas (1) and (2) and a homopolymer containing constituent units represented by general formula (3), or may be a blend containing Copolymers of constituent units represented by formulas (1) and (2) and copolymers containing constituent units represented by general formulas (1) and (3).

The polycarbonate resin of the present invention may contain any of random, block and alternating copolymerization structures.

The polycarbonate resin of the present invention preferably has a polystyrene-equivalent weight average molecular weight (Mw) of 20,000 to 200,000.

More preferably, the weight average molecular weight (Mw) in terms of polystyrene is 25,000 to 120,000, still more preferably 28,000 to 55,000, most preferably 30,000 to 45,000.

When Mw is less than 20,000, the formed body becomes brittle, which is unfavorable. When the Mw exceeds 200,000, the melt viscosity becomes high, so it becomes difficult to take out the resin after manufacture, and the fluidity deteriorates, making injection molding in a molten state difficult, which is unfavorable.

The polycarbonate resin of the present invention has a refractive index (nD) at 23°C and a wavelength of 589 nm, preferably 1.635-1.695, more preferably 1.640-1.690, still more preferably 1.645-1.685, and most preferably 1.670-1.685. The polycarbonate resin of the present invention has a high refractive index (nD) and is suitable for optical lens materials. For a film with a thickness of 0.1 mm, the refractive index can be measured by the method of JIS-K-7142 using an Abbe refractometer.

The Abbe number (ν) of the polycarbonate resin of the present invention is preferably 24 or less, more preferably 22 or less, still more preferably 20 or less. The Abbe's number can be calculated using the following formula from the refractive indices at wavelengths of 486 nm, 589 nm, and 656 nm at 23°C. ν=(nD-1)/(nF-nC) nD: Refractive index at a wavelength of 589nm nC: Refractive index at a wavelength of 656nm nF: Refractive index at a wavelength of 486nm

Other resins can be blended with the polycarbonate resin of the present invention for the manufacture of molded objects. Other resins include, for example, polyamide, polyacetal, polycarbonate, modified polyphenylene ether, polyethylene terephthalate, polybutylene terephthalate, and the like.

Furthermore, in the polycarbonate resin of the present invention, antioxidants, mold release agents, ultraviolet absorbers, fluidity modifiers, crystallization nucleating agents, strengthening agents, dyes, antistatic agents or antibacterial agents can be added.

The molding method includes, but is not limited to, compression molding, casting, roll processing, extrusion molding, stretching, etc. other than injection molding.

When the polycarbonate resin of the present invention is used for injection molding, the preferred glass transition temperature (Tg) is 90-180°C, more preferably 95-175°C, more preferably 100-170°C, and still more preferably 130-170°C, especially 135-150°C. When Tg is lower than 90° C., the usable temperature range becomes narrow, which is not preferable. Also, when the temperature exceeds 180°C, the melting temperature of the resin increases, and the decomposition or coloring of the resin tends to occur, which is not preferable. When the glass transition temperature of the resin is too high, the difference between the mold temperature and the glass transition temperature of the resin will increase when using a general-purpose mold temperature controller. Therefore, resins with an excessively high glass transition temperature are difficult to use in applications that require strict surface accuracy of products, which is not preferable. Also, from the viewpoint of molding fluidity and molding heat resistance, the lower limit of Tg is preferably 130°C, more preferably 135°C; the upper limit of Tg is preferably 160°C, more preferably 150°C.

The optical molding obtained by using the polycarbonate resin of the present invention preferably has a total light transmittance of 85% or more, more preferably 88% or more. If the total light transmittance is 85% or more, it is not inferior to bisphenol A polycarbonate resin and the like.

The polycarbonate resin of the present invention has high moisture and heat resistance. Moisture and heat resistance can be evaluated by performing a "PCT test" (pressure cooker test) on an optical molding obtained using a polycarbonate resin, and measuring the total light transmittance of the optical molding after the test. The PCT test can be carried out by keeping an injection molded product with a diameter of 50mm and a thickness of 3mm at 120°C, 0.2Mpa, 100%RH, and 20 hours. The polycarbonate resin of the present invention has a total light transmittance after the PCT test of 60% or more, preferably 70% or more, more preferably 75% or more, more preferably 80% or more, and most preferably 85% or more. If the total light transmittance is 60% or more, it can be said to have high moisture and heat resistance compared to conventional polycarbonate resins.

The b value of the polycarbonate resin of the present invention is preferably 5 or less. The smaller the b value, the weaker the yellow tone and the better the hue.

The amount of residual phenol contained in the polycarbonate resin of the present invention is preferably at most 500 ppm, more preferably at most 300 ppm, and still more preferably at most 50 ppm.

The amount of residual diphenyl carbonate (DPC) contained in the polycarbonate resin of the present invention is preferably 200 ppm or less, more preferably 100 ppm or less, still more preferably 50 ppm or less.

(通式(4)中，X表示碳數1～4之伸烷基，a及b各自獨立地表示1～10之整數)。 表示之化合物作為二羥基成分，且與碳酸二酯等之碳酸酯前驅物質反應而得到的樹脂。但是，製造樹脂時，係可能有由上述通式(4)之化合物產生具有下述式(A)表示之末端構造的聚合物及式(B)表示之化合物作為副生成物，而含有於本發明之聚碳酸酯樹脂中的情況，又或者得到式(1)之聚合物後，末端改質為乙烯基，而成為具有下述式(A)表示之末端構造的聚合物的情況。

[式(A)及(B)中， X表示碳數1～4之伸烷基， a及b各自獨立地表示1～10之整數， Hm分別為氫原子， *為聚合物鏈]。 (Amount of Vinyl Terminal Groups) The polycarbonate resin of the present invention is obtained by using the following general formula (4) as described later.

(In the general formula (4), X represents an alkylene group having 1 to 4 carbon atoms, and a and b each independently represent an integer of 1 to 10). The indicated compound is a resin obtained by reacting a dihydroxy component with a carbonate precursor such as a carbonic acid diester. However, when the resin is produced, there may be a polymer having a terminal structure represented by the following formula (A) and a compound represented by the formula (B) as by-products from the compound of the above general formula (4), which are contained in this product. In the case of the polycarbonate resin of the invention, or after the polymer of formula (1) is obtained, the terminal is modified into a vinyl group to obtain a polymer having a terminal structure represented by the following formula (A).

[In the formulas (A) and (B), X represents an alkylene group having 1 to 4 carbon atoms, a and b each independently represent an integer of 1 to 10, Hm represents a hydrogen atom, and * represents a polymer chain].

According to a preferred aspect of the present invention, when measuring the H ¹ -NMR spectrum of the polycarbonate resin, the polymer having the terminal structure represented by the general formula (A) contained in the polycarbonate resin and the general formula (B) The total content of the indicated compounds is preferably an amount that satisfies the following relationship (that is, "amount of fennel-based vinyl terminal group 1").

The amount 1 of the fenene-based vinyl end group calculated by the formula (I) is more preferably 0.001-0.8, particularly preferably 0.01-0.5. It is preferable that the polycarbonate resin has excellent fluidity and strength, such as flexural strength and tensile strength, when the amount 1 of the vinyl end group calculated by the formula (I) is within the above range.

Formula (I) corresponds to the following formula.

In the above formula, "Ha derived from the repeating unit of the compound of formula (4)" means all hydrogen atoms contained in X of formula (4). For example, when X is an ethylenyl group, the position of Ha is as follows. Furthermore, when the compound represented by the general formula (5) and/or (6) is further used as the dihydroxy component, "Hb derived from the repeating unit of the compound of the formula (5)" and "the repeating unit derived from the compound of the formula (6) The integral value of "Hc" in is added to the denominator of the above formula, which will be described later.

Here, "integrated value of proton peak" and "integrated value of peak" refer to the signal of NMR spectrum when NMR spectrum ( ¹ H-NMR spectrum) of proton ¹ H is measured by NMR (nuclear magnetic resonance) spectroscopy. The area value, that is, the integral value. In general, NMR spectroscopy is a measurement method focusing on the nucleus of a substance, and can quantitatively measure the nucleus itself constituting each molecule. That is, in the case of ¹ H-NMR, the integrated value of the observed signal indicates the abundance of ¹ H in the molecule. In the present invention, the assignment of ¹ H is estimated from the chemical shift value of ¹ H-NMR spectrum, and the integral value of ¹ H signal is obtained for each chemical shift value.

(通式(5)中，Y表示碳數1～4之伸烷基，c及d各自獨立地表示1～10之整數)；

(通式(6)中， Z表示碳數1～4之伸烷基， R ₁～R ₆係各自獨立地表示氫原子、碳數1～20之烷基、碳數1～20之烷氧基、碳數5～20之環烷基、碳數5～20之環烷氧基、碳數6～20之芳基或碳數6～20之芳氧基，e及f各自獨立地表示0～5之整數)。 表示之化合物作為二羥基成分，且與碳酸二酯等之碳酸酯前驅物質反應以得到的樹脂。但是，製造如此之樹脂時，可能有由上述通式(5)及/或(6)之化合物產生具有下述式(C)及/或(E)表示之末端構造的聚合物及式(D)及/或(F)表示之化合物作為副生成物，而含有於本發明之聚碳酸酯樹脂中的情況，又或者得到聚合物之後，末端改質為乙烯基，而成為具有下述式(C)及/或(E)表示之末端構造的聚合物的情況。

[式(C)～(F)中， Y及Z各自獨立地表示碳數1～4之伸烷基， R ₁～R ₆係各自獨立地表示氫原子、碳數1～20之烷基、碳數1～20之烷氧基、碳數5～20之環烷基、碳數5～20之環烷氧基、碳數6～20之芳基或碳數6～20之芳氧基， c及d各自獨立地表示1～10之整數， e表示1～5之整數， f表示0～5之整數，且f-1為0以上， Hn及Hо分別為氫原子， *為聚合物鏈]。 The polycarbonate resin of the present invention preferably uses the following general formula (5) and/or (6) in addition to the compound represented by the above general formula (4).

(In the general formula (5), Y represents an alkylene group with 1 to 4 carbon atoms, and c and d each independently represent an integer of 1 to 10);

(In general formula (6), Z represents an alkylene group with 1 to 4 carbons, R ₁ to R ₆ each independently represent a hydrogen atom, an alkyl group with 1 to 20 carbons, an alkoxy group with 1 to 20 carbons radical, cycloalkyl with 5 to 20 carbons, cycloalkoxy with 5 to 20 carbons, aryl with 6 to 20 carbons or aryloxy with 6 to 20 carbons, e and f each independently represent 0 ~ an integer of 5). Resin obtained by reacting the indicated compound as a dihydroxy component with a carbonate precursor such as carbonic acid diester. But, when making such a resin, there may be a polymer with a terminal structure represented by the following formula (C) and/or (E) and the formula (D) from the compound of the above general formula (5) and/or (6). ) and/or (F) as a by-product and contained in the polycarbonate resin of the present invention, or after the polymer is obtained, the terminal is modified into a vinyl group, and the following formula ( In the case of polymers with terminal structures represented by C) and/or (E).

[In formulas (C) to (F), Y and Z each independently represent an alkylene group with 1 to 4 carbons, and R ₁ to R ₆ each independently represent a hydrogen atom, an alkyl group with 1 to 20 carbons, Alkoxy with 1 to 20 carbons, cycloalkyl with 5 to 20 carbons, cycloalkoxy with 5 to 20 carbons, aryl with 6 to 20 carbons or aryloxy with 6 to 20 carbons, c and d each independently represent an integer of 1 to 10, e represents an integer of 1 to 5, f represents an integer of 0 to 5, and f-1 is 0 or more, Hn and Hо are hydrogen atoms, respectively, and * is a polymer chain ].

According to a preferred aspect of the present invention, when measuring the H ¹ -NMR spectrum of the polycarbonate resin, the polymer having the terminal structure represented by the general formula (C) contained in the polycarbonate resin and the general formula (D) The total content of the indicated compounds is preferably an amount that satisfies the following relationship (that is, "the amount of binaphthol-based vinyl terminal groups").

The amount of binaphthol-based vinyl terminal groups calculated by the formula (II) is more preferably 0.05-0.8, particularly preferably 0.1-0.6. When the amount of binaphthol-based vinyl end groups calculated by the formula (II) is within the above range, the polycarbonate resin has excellent fluidity and strength, which is preferable.

Formula (II) corresponds to the following formula.

In the above formula, "from the Hb in the repeating unit of the compound of formula (5)" and "from the Hc in the repeating unit of the compound of formula (6)" mean Y and Z in the formulas (5) and (6) respectively all the hydrogen atoms contained in it. For example, when Y and Z are ethylenyl groups, the positions of Hb and Hc are as follows, respectively.

According to a preferred aspect of the present invention, when measuring the H ¹ -NMR spectrum of the polycarbonate resin, the polymer having the terminal structure represented by the general formula (E) contained in the polycarbonate resin and the general formula (F) The total content of the indicated compounds is preferably an amount that satisfies any of the following relationships (that is, "amount of fennel-based vinyl terminal groups 2" and "amount of fennel-based vinyl terminal groups 3").

Here, when R ₁ to R ₄ in formulas (5'), (E) and (F) are not aryl groups with 6 to 20 carbons and aryloxy groups with 6 to 20 carbons, the above formulas apply (III), when at least one of R ₁ to R ₄ in formulas (5'), (E) and (F) is an aryl group with 6 to 20 carbons or an aryloxy group with 6 to 20 carbons, it is applicable The above formula (IV).

The amount 2 of the fenene-based vinyl end group calculated by the formula (III) is more preferably 0.001-0.8, particularly preferably 0.01-0.5. It is preferable that the polycarbonate resin has excellent fluidity and strength when the amount 2 of the fennel-based vinyl end group calculated by the formula (III) is within the above-mentioned range.

The amount 3 of the vinyl end group of the stilbene system calculated by the formula (IV) is more preferably 0.001-0.8, particularly preferably 0.01-0.5. It is preferable that the polycarbonate resin has excellent fluidity and strength when the amount 3 of the fennel-based vinyl terminal groups calculated by the formula (IV) is within the above-mentioned range.

Formulas (III) and (IV) correspond to the following formulas.

(通式(4)中，X表示碳數1～4之伸烷基，a及b各自獨立地表示1～10之整數)。 表示之化合物作為二羥基成分，且與碳酸二酯等之碳酸酯前驅物質反應而製造。具體而言，可將通式(4)表示之化合物及碳酸二酯等之碳酸酯前驅物質，於鹼性化合物觸媒或酯交換觸媒或由其雙方所構成的混合觸媒之存在下，或無觸媒下，藉由熔融聚縮合法反應來製造。 (2) Production method of polycarbonate resin The polycarbonate resin having the structural unit represented by the general formula (1) of the present invention can use the following general formula (4)

(In the general formula (4), X represents an alkylene group having 1 to 4 carbon atoms, and a and b each independently represent an integer of 1 to 10). The indicated compound is produced by reacting with a carbonate precursor such as a carbonic acid diester as a dihydroxy component. Specifically, the compound represented by general formula (4) and carbonate precursors such as carbonic diester can be used in the presence of a basic compound catalyst or a transesterification catalyst or a mixed catalyst composed of both of them, Or without a catalyst, it can be produced by melt polycondensation reaction.

The compounds of the general formula (4) include 9,9-bis(hydroxy(poly)alkoxynaphthyl) terfenenes. For example, compounds of general formula (4) include 9,9-bis[6-(1-hydroxymethoxy)naphthalene-2-yl] fennel, 9,9-bis[6-(2-hydroxyethoxy Base) naphthalene-2-yl] fennel, 9,9-bis[6-(3-hydroxypropoxy)naphthalene-2-yl] terme, and 9,9-bis[6-(4-hydroxybutoxy ) Naphthalene-2-yl] fennel, etc. Among them, 9,9-bis[6-(2-hydroxyethoxy)naphthalen-2-yl]tertilene is preferred. These may be used alone or in combination of two or more.

When the compound of the general formula (4) is produced, as an impurity, a compound in which any one of a and b is 0 may be by-produced as an impurity. The content of such impurities is preferably at most 1000 ppm, more preferably at most 500 ppm, still more preferably at most 200 ppm, and most preferably at most 100 ppm in the monomer containing the compound of general formula (4) as the main component. Furthermore, in addition to such impurities, tergenone, one of the raw materials, may also be included as an impurity. The content of tertilone is preferably not more than 1000 ppm, more preferably not more than 100 ppm, more preferably not more than 50 ppm, and most preferably not more than 10 ppm, in the monomer mainly composed of the compound of general formula (4). The tergenone contained in the monomer containing the compound of the general formula (4) as the main component may remain in the resin after polymerization. The lower the content of tertilone, the better the hue of the resin, so it is better. Furthermore, although it is not an impurity, the compound whose a and b in the general formula (4) are different (that is, a≠b) is preferably combined in a monomer whose main component is the compound of the general formula (4). It is 50 ppm or less, more preferably 20 ppm or less.

The compound of general formula (4) can be produced by various synthetic methods. For example, as described in Japanese Patent No. 5442800, (a) in the presence of hydrogen chloride gas and mercaptocarboxylic acid, the method of making perylenes and hydroxynaphthalenes react, (b) in an acid catalyst (and In the presence of alkylthiol), the method of reacting 9-tilone with hydroxynaphthalene, (c) in the presence of hydrochloric acid and mercaptans (mercaptocarboxylic acid, etc.) The method, (d) in the presence of sulfuric acid and mercaptans (mercaptocarboxylic acid, etc.), react fluorenones and hydroxynaphthalenes, and carry out crystallization with a crystallization solvent composed of hydrocarbons and polar solvents to produce The method of bis-naphthol stilbene, etc., to obtain 9,9-bis(hydroxynaphthyl) stilbene, and make it react with the compound corresponding to [XO]a group and [XO]b group (alkylene oxide or haloalkanol, etc. ) reaction to manufacture. For example, 9,9-bis[6-(2-hydroxyethoxy)naphthyl]tilene can be obtained by reacting 9,9-bis[6-hydroxynaphthyl]tilene with 2-chloroethanol under alkaline conditions And get.

The polycarbonate resin having the constituent units represented by the general formula (1) of the present invention can be used in combination with an aromatic dihydroxy compound or an aliphatic dihydroxy compound (such as a dihydroxy compound having a skeletal skeleton) in addition to the compound of the general formula (4). hydroxy compounds or binaphthols) as the dihydroxy component.

(通式(5)中，Y表示碳數1～4之伸烷基，c及d各自獨立地表示1～10之整數)。

(通式(6)中， Z表示碳數1～4之伸烷基， R ₁～R ₆係各自獨立地表示氫原子、碳數1～20之烷基、碳數1～20之烷氧基、碳數5～20之環烷基、碳數5～20之環烷氧基、碳數6～20之芳基或碳數6～20之芳氧基， e及f各自獨立地表示0～5之整數)。 Preferably, the polycarbonate resin of the present invention, in addition to the compound represented by the above-mentioned general formula (4), can use the compound represented by the following general formula (5) and/or the compound represented by the following general formula (6) as Dihydroxy components to manufacture.

(In the general formula (5), Y represents an alkylene group having 1 to 4 carbon atoms, and c and d each independently represent an integer of 1 to 10).

(In general formula (6), Z represents an alkylene group with 1 to 4 carbons, R ₁ to R ₆ each independently represent a hydrogen atom, an alkyl group with 1 to 20 carbons, an alkoxy group with 1 to 20 carbons radical, cycloalkyl with 5 to 20 carbons, cycloalkoxy with 5 to 20 carbons, aryl with 6 to 20 carbons or aryloxy with 6 to 20 carbons, e and f each independently represent 0 ~ an integer of 5).

Examples of dihydroxy compounds represented by formula (5) include 2,2'-bis(1-hydroxymethoxy)-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy )-1,1'-binaphthyl, 2,2'-bis(3-hydroxypropoxy)-1,1'-binaphthyl, 2,2'-bis(4-hydroxybutoxy)-1, 1'-binaphthyl, etc. Among them, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene (hereinafter abbreviated as "BHEBN") is preferred. These may be used alone or in combination of two or more.

When producing the compound of the general formula (5), as an impurity, a compound in which any one of c and d is 0 may be by-produced as an impurity. The total content of such impurities is preferably at most 1000 ppm, more preferably at most 500 ppm, further preferably at most 200 ppm, and most preferably at most 100 ppm in the monomer mainly composed of the compound of general formula (5). Furthermore, although it is not an impurity, the compound whose c and d in the general formula (5) are not the same (that is, c≠d) is preferably combined in a monomer whose main component is the compound of the general formula (5) It is 50 ppm or less, more preferably 20 ppm or less.

Examples of dihydroxy compounds represented by formula (6) include 9,9-bis[4-(2-hydroxyethoxy)phenyl] fennel, 9,9-bis[4-(2-hydroxyethoxy )-3-methylphenyl] terrene, 9,9-bis[4-(2-hydroxyethoxy)-3-tert-butylphenyl] terrene, 9,9-bis[4-(2- Hydroxyethoxy)-3-isopropylphenyl] terme, 9,9-bis[4-(2-hydroxyethoxy)-3-cyclohexylphenyl] terme, 9,9-bis[4- (2-Hydroxyethoxy)-3-phenylphenyl] fennel (hereinafter abbreviated as "BPPEF") and the like. Among them, 9,9-bis[4-(2-hydroxyethoxy) phenyl] fennel and 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl] terrene are the most important good. These may be used alone or in combination of two or more.

When producing the compound of the general formula (6), as an impurity, a compound in which any one of e and f is 0 may be by-produced as an impurity. The total content of such impurities is preferably at most 1000 ppm, more preferably at most 500 ppm, further preferably at most 200 ppm, and most preferably at most 100 ppm in the monomer mainly composed of the compound of general formula (6). Further, although it is not an impurity, the compound whose e and f in the general formula (6) are not the same (that is, e≠f) is preferably combined in a monomer whose main component is the compound of the general formula (6). It is 50 ppm or less, more preferably 20 ppm or less.

In addition to the above, aromatic dihydroxy compounds that can be used in combination are, for example, bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol Phenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC and bisphenol Z, etc.

Carbonic acid diester used in the present invention can enumerate diphenyl carbonate, xylyl carbonate, two (chlorophenyl) carbonates, m-cresol carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate , Dicyclohexyl carbonate, etc. Among them, diphenyl carbonate is particularly preferable. The diphenyl carbonate is preferably used in a ratio of 0.97 to 1.20 moles, more preferably in a ratio of 0.98 to 1.10 moles, relative to 1 mole of the total of dihydroxy compounds.

Among the transesterification catalysts, the basic compound catalyst particularly includes alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and the like.

The alkali metal compound used in the present invention includes, for example, organic acid salts, inorganic salts, oxides, hydroxides, hydrides, or alkoxides of alkali metals. Specifically, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, Sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium boronate phenylate, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, sodium hydrogen phosphate , 2 potassium hydrogen phosphate, 2 lithium hydrogen phosphate, 2 sodium phenyl phosphate, 2 sodium salt, 2 potassium salt, 2 cesium salt or 2 lithium salt of bisphenol A, sodium salt, potassium salt, cesium salt or lithium salt of phenol Wait.

Examples of alkaline earth metal compounds include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkaline earth metal compounds. Specifically, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogencarbonate, calcium hydrogencarbonate, strontium hydrogencarbonate, barium hydrogencarbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, Magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenyl phosphate, etc.

Examples of nitrogen-containing compounds include quaternary ammonium hydroxides, salts thereof, and amines. Specifically, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, etc. having an alkyl or aryl group can be used. 4-grade ammonium hydroxides such as triethylamine, dimethylbenzylamine, triphenylamine, etc. 3-grade amines; diethylamine, dibutylamine, etc. 2-grade amines; Primary amines such as base amine and butyl amine; imidazoles such as 2-methylimidazole, 2-phenylimidazole and benzimidazole; or ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, Alkali or basic salts of tetrabutylammonium tetraphenylborate, tetraphenylammonium tetraphenylborate, etc.

As the transesterification catalyst, it is preferable to use salts of zinc, tin, zirconium, lead, etc., and these can be used alone or in combination.

As a transesterification catalyst, specifically, zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin(II) chloride, tin(IV) chloride, tin(II) acetate, tin(IV) acetate can be used , dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconyl acetate, zirconium tetrabutoxide, lead (II) acetate, lead (IV) acetate, etc.

These catalysts may be used at a ratio of 1×10 ^-9 to 1×10 ^-3 mol, preferably 1×10 ^-7 to 1×10 ^-4 , relative to the total 1 mol of the dihydroxy compound Mole's ratio is used.

The melt polycondensation method is to use the above-mentioned raw materials and catalysts to carry out transesterification reaction under heating under normal pressure or reduced pressure to remove by-products while performing melt polycondensation.

In the melt polycondensation in this composition system, it is preferable to melt the compound represented by the general formula (4) and the carbonic acid diester in a reaction vessel, and react in a state where the by-produced monohydroxyl compound remains. In order to make it stagnate, the reaction apparatus can be closed, depressurized or pressurized, etc., and can control pressure. The reaction time of this step is not less than 20 minutes and not more than 240 minutes, preferably not less than 40 minutes and not more than 180 minutes, particularly preferably not less than 60 minutes and not more than 150 minutes. At this time, if the by-produced monohydroxyl compound is distilled off immediately after production, the finally obtained polycarbonate resin will have a small amount of high molecular weight body. However, if the by-produced monohydroxyl compound is allowed to stay in the reaction vessel for a certain period of time, the polycarbonate resin finally obtained can be obtained with a large content of high molecular weight body.

The melt polycondensation reaction may be carried out continuously or batch-wise. The reaction device used when carrying out the reaction can be a longitudinal type equipped with anchor type stirring blades, Maxblend stirring blades, helical ribbon type stirring blades, etc.; Horizontal type; it can also be an extrusion type equipped with a screw. In addition, it is suitable to use a reaction device in which these reaction devices are properly combined in consideration of the viscosity of the polymer.

In the production method of the polycarbonate resin used in the present invention, after the polymerization reaction is completed, in order to maintain thermal stability and hydrolytic stability, the catalyst may also be removed or deactivated. A method of deactivating a catalyst by adding a known acidic substance can be suitably implemented. As the acidic substance, specifically, esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, and aromatic sulfonic acids such as p-butyl toluenesulfonate and p-hexyl toluenesulfonate can be suitably used. Esters; phosphoric acid such as phosphorous acid, phosphoric acid, phosphonic acid, etc.; triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, diphosphite Phosphites such as n-butyl, di-n-hexyl phosphite, dioctyl phosphite, monooctyl phosphite, etc.; triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate Phosphonic acid esters such as dioctyl phosphate and monooctyl phosphate; phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, and dibutylphosphonic acid; phosphonic esters such as diethyl phenylphosphonate Phosphines such as triphenylphosphine and bis(diphenylphosphino)ethane; boric acids such as boric acid and phenylboronic acid; aromatic sulfonic acids such as tetrabutylphosphonium dodecylbenzenesulfonate Salts; organic halides such as stearic acid chloride, benzoyl chloride, p-toluenesulfonic acid chloride, etc.; alkyl sulfuric acid such as dimethyl sulfuric acid; organic halides such as benzyl chloride, etc. These deactivators are used at 0.01-50 times mole, preferably at 0.3-20 times mole, relative to the catalyst amount. When it is less than 0.01 mole with respect to the catalyst amount, the deactivation effect becomes insufficient, which is unfavorable. Also, when the amount is more than 50 times the amount of the catalyst, the heat resistance of the resin is lowered, and the molded article is likely to be colored, which is not preferable.

After the catalyst is deactivated, a step of volatilizing and removing the low-boiling compounds in the polymer at a pressure of 0.1-1 mmHg and a temperature of 200-350°C can also be set. In this step, a horizontal device equipped with stirring wings excellent in surface renewal ability such as paddle-shaped wings, lattice-shaped wings, and spectacle-shaped wings, or a thin-film evaporator can be used suitably.

The polycarbonate resin of the present invention is expected to contain extremely little foreign matter, and is suitable for filtering molten raw materials, filtering catalyst liquids, and the like. The mesh of the filter is preferably 5 μm or less, more preferably 1 μm or less. Furthermore, it is suitable to carry out filtering the produced resin with a polymer filter. The mesh of the polymer filter is preferably 100 μm or less, more preferably 30 μm or less. Also, the step of taking resin pellets must be of course in a low-dust environment, preferably level 6 or less, more preferably level 5 or less.

In another aspect of the present invention, when producing polycarbonate resins containing structural units represented by general formulas (1) to (3) or polycarbonate resins containing structural units represented by general formulas (1) and (2) , compounds represented by general formulas (4) to (6) can be used to produce copolymers comprising constituent units represented by general formulas (1) to (3) or constituent units represented by general formulas (1) and (2); Compounds represented by the general formulas (4) to (6) can also be polymerized separately to produce a ternary resin or a binary resin including homopolymers composed of respective constituent units. Alternatively, blending may be performed after polymerizing a copolymer comprising constituent units represented by general formulas (1) and (2) and a homopolymer comprising constituent units represented by general formula (3), or may be blended after polymerizing a copolymer comprising constituent units represented by general formula The copolymers of the constituent units represented by (1) and (2) and the copolymers containing the constituent units represented by the general formulas (1) and (3) are polymerized and blended.

(3) Optical molding An optical molded article can be produced using the polycarbonate resin of the present invention. For example, it can be molded by any method such as injection molding, compression molding, extrusion molding, or solution casting. Since the polycarbonate resin of the present invention is excellent in formability and heat resistance, it can be used particularly advantageously in optical lenses requiring injection molding. The polycarbonate resin of the present invention may be mixed with other resins such as other polycarbonate resins or polyester resins during molding. In addition, antioxidants, process stabilizers, light stabilizers, polymerized metal inactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, mold release agents, ultraviolet absorbers, and plasticizers can also be mixed , phase solvent and other additives.

Antioxidants include triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis[3-( 3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] , octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-paraffin (3, 5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 3, 5-di-tert-butyl-4-hydroxy-benzyl phosphonate-diethyl ester, ginseng (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and 3 ,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4, 8,10-tetraoxaspiro(5,5)undecane, etc. The content of the antioxidant in the polycarbonate resin is preferably 0.001 to 0.3 parts by weight with respect to 100 parts by weight of the polycarbonate resin.

Examples of the processing stabilizer include phosphorus-based processing heat stabilizers, sulfur-based processing heat stabilizers, and the like. Examples of phosphorus-based processing heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specifically, triphenyl phosphite, ginseng (nonylphenyl) phosphite, ginseng (2,4-di-tert-butylphenyl) phosphite, ginseng (2,6-di- tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite , diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis(2,6-di-tert-butyl -4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, bis(nonylphenyl)pentaerythritol diphosphite Phosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol Diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenylmonoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, phosphoric acid Diisopropyl ester, dimethyl phenyl phosphonate, diethyl phenyl phosphonate, dipropyl phenyl phosphonate, tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenyl Phosphonite, tetrakis(2,4-di-t-butylphenyl)-4,3'-biphenyldiphosphonite, tetrakis(2,4-di-t-butylphenyl)- 3,3'-biphenyl diphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenyl phosphonite and bis(2,4-bis -tert-butylphenyl)-3-phenyl-phenyl ester and the like. The content of the phosphorus-based processing heat stabilizer in the polycarbonate resin is preferably 0.001 to 0.2 parts by weight relative to 100 parts by weight of the polycarbonate resin.

Sulfur-based processing heat stabilizers, such as pentaerythritol-tetrakis (3-lauryl thiopropionate), pentaerythritol-tetrakis (3-myristyl thiopropionate), pentaerythritol-tetrakis (3-stearyl thiopropionate) propionate), dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thio On behalf of dipropionate and so on. The content of the sulfur-based processing heat stabilizer in the polycarbonate resin is preferably 0.001 to 0.2 parts by weight relative to 100 parts by weight of the polycarbonate resin.

The release agent is preferably composed of esters of alcohols and fatty acids in an amount of 90% by weight or more. Esters of alcohols and fatty acids specifically include esters of monohydric alcohols and fatty acids, or partial or full esters of polyhydric alcohols and fatty acids. The above-mentioned ester of a monohydric alcohol and a fatty acid is preferably an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Also, the partial or full ester of a polyhydric alcohol and a fatty acid is preferably a partial or full ester of a polyhydric alcohol having 1 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms.

Specifically, esters of monohydric alcohols and saturated fatty acids include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, and isopropyl palmitate. Partial or full esters of polyhydric alcohols and saturated fatty acids, such as stearic acid monoglyceride, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, Monoglyceryl Behenate, Monoglyceryl Caprate, Monoglyceryl Laurate, Pentaerythritol Monostearate, Pentaerythritol Tetrastearate, Pentaerythritol Tetranonanoate, Propylene Glycol Monostearate, Biphenyl Full or partial esters of dipentaerythritol such as biphenol ester, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate, etc. The content of these release agents is preferably in the range of 0.005 to 2.0 parts by weight, more preferably in the range of 0.01 to 0.6 parts by weight, and still more preferably in the range of 0.02 to 0.5 parts by weight, relative to 100 parts by weight of the polycarbonate resin. range of servings.

The ultraviolet absorber is preferably selected from the group consisting of benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, cyclic imide ester-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers. At least one ultraviolet absorber of the group of absorbers. That is, the ultraviolet absorbers listed below may be used alone or in combination of two or more.

Benzotriazole-based UV absorbers include 2-(2-hydroxy-5-methylphenyl)benzotriazole and 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole , 2-(2-hydroxy-3,5-diisopropylphenylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5 -Chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol ], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5- Chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-pentylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole Azole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octyloxyphenyl)benzotriazole, 2,2'-methylene Basebis(4-isopropylphenyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazin-4-one), 2-[2 -Hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, etc.

Benzophenone-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-Hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfur Oxytrihydridrate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxybenzophenone Hydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis(5-benzyl Acyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxydi Benzophenone etc.

Triazine UV absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-(4 , 6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-[(octyl)oxy]-phenol, etc.

Cyclic imide ester UV absorbers, such as 2,2'-bis(3,1-benzoxazin-4-one), 2,2'-p-phenylene bis(3,1-benzene oxazin-4-one), 2,2'-m-phenylene bis(3,1-benzoxazin-4-one), 2,2'-(4,4'-diphenylene ) bis(3,1-benzoxazin-4-one), 2,2'-(2,6-naphthalene)bis(3,1-benzoxazin-4-one), 2,2'- (1,5-naphthalene)bis(3,1-benzoxazin-4-one), 2,2'-(2-methyl-p-phenylene)bis(3,1-benzoxazine -4-one), 2,2'-(2-nitro-p-phenylene)bis(3,1-benzoxazin-4-one) and 2,2'-(2-chloro-p -phenylene)bis(3,1-benzoxazin-4-one) and the like.

Cyanoacrylate UV absorbers include 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2 -cyano-3,3-diphenylacryl)oxy]methyl)propane, and 1,3-bis-[(2-cyano-3,3-diphenylacryl)oxy ] Benzene etc.

The content of the ultraviolet absorber is preferably from 0.01 to 3.0 parts by weight, more preferably from 0.02 to 1.0 parts by weight, and still more preferably from 0.05 to 0.8 parts by weight, based on 100 parts by weight of the polycarbonate resin. If it is the range of this compounding quantity, sufficient weather resistance can be provided to a polycarbonate resin according to a use.

The polycarbonate resin of the present invention has high refractive index and low Abbe number. Furthermore, in addition to optical lenses, transparent conductive substrates, optical discs, liquid crystal panels, optical cards, sheets, films, optical fibers, connectors, etc. suitable for liquid crystal displays, organic EL displays, solar cells, etc. Optical moldings for structural materials or functional materials of optical parts such as vapor-deposited plastic mirrors and displays.

On the surface of the optical molded body, coatings such as anti-reflection layer or hard coating can also be provided as required. The anti-reflection layer can be a single layer or a multilayer, can be organic or inorganic, and is preferably inorganic. Specifically, oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide, and magnesium fluoride are exemplified.

(4) Optical lens The optical lens manufactured by using the polycarbonate resin of the present invention has high refractive index, low Abbe number, and high moisture and heat resistance, so it can be used in telescopes, binoculars, TV projectors, etc. The field of glass lenses is extremely useful. It is preferable to use it in the shape of an aspheric lens as required. The aspherical lens system can make the spherical aberration substantially zero with one lens, so it is not necessary to remove the spherical aberration by combining a plurality of spherical lenses, and can achieve weight reduction and production cost reduction. Therefore, aspherical lenses are especially useful as camera lenses among optical lenses. The optical lens is molded by arbitrary methods such as injection molding, compression molding, and injection compression molding, for example. By means of the present invention, the aspheric lens with high refractive index and low birefringence that is technically difficult to process with glass lens can be obtained more easily.

In order to prevent foreign matter from entering the optical lens as much as possible, the molding environment must also be a low-dust environment, preferably grade 6 or less, more preferably grade 5 or less.

(5) Optical film The optical film produced by using the polycarbonate resin of the present invention has excellent transparency and heat resistance, so it is suitable for use in films for liquid crystal substrates, optical memory cards, and the like.

In order to prevent foreign matters from entering the optical film as much as possible, the forming environment must also be a low-dust environment, preferably a grade 6 or lower, more preferably a grade 5 or lower.

流速：0.3ml/分 管柱溫度：45℃ 檢測器：UV(225nm) 測定裝置(MS部分)：Agilent 6120 single quad LCMS System 離子化源：ESI 極性：Positive 碎裂電壓：100V 乾氣：10L/分、350℃ 噴霧器：50psi 毛細管電壓：3000V 測定離子： BHEBN：離子種=[M+NH ⁴] ^-、m/z=392.1 BPPEF：離子種=[M+NH ⁴] ^-、m/z=608.3 10)成形性：於上述b值之測定，於成形時基於下述基準來評估成形性。 A：成形片無空隙、表面無波狀起伏。 B：成形片有空隙。 C：成形片之表面有波狀起伏。 D：成形片有空隙、表面有變形。 11)PCT(壓力鍋試驗)：將直徑50mm、厚度3mm之射出成形物，以HIRAYAMA公司製 PC-305SIII，以120℃、0.2Mpa、100%RH、20小時之條件保持後，取出樣品，使用日本電色工業(股)製 SE2000型分光式色差計，以JIS-K-7361-1之方法測定。 <Examples> The present invention will be described below using examples, but the present invention is not limited by these examples. In addition, the measured value in an Example was measured using the following method or apparatus. 1) Polystyrene-equivalent weight-average molecular weight (Mw): Use gel permeation chromatography (GPC) with tetrahydrofuran as the developing solvent, and use standard polystyrene with known molecular weight (molecular weight distribution = 1) to make a calibration curve. Based on this calibration curve, Mw was calculated from the residence time of GPC. 2) Refractive index (nD): Measured by the method of JIS-K-7142 using an Abbe refractometer for a 0.1 mm-thick film made of the polycarbonate resin produced in the examples. 3) Abbe's number (ν): For a film with a thickness of 0.1mm made of the polycarbonate resin produced in the example, use an Abbe refractometer to measure the refractive index at 23°C at wavelengths of 486nm, 589nm and 656nm, Furthermore, Abbe's number was calculated using the following formula. ν=(nD-1)/(nF-nC) nD: Refractive index at wavelength 589nm nC: Refractive index at wavelength 656nm nF: Refractive index at wavelength 486nm 4) Glass transition temperature (Tg): Differential thermal scanning Calorimeter (DSC) measurement. 5) Total light transmittance: For a plate with a thickness of 3 mm made of polycarbonate resin for the measurement of the following b value, use the SE2000 spectroscopic color difference meter manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS-K -7361-1 method determination. 6) b value: After vacuum-drying the produced resin at 120°C for 4 hours, injection molding is performed with an injection molding machine (FANUC ROBOSHOT α-S30iA) at a cylinder temperature of 270°C and a mold temperature of Tg-10°C to obtain the diameter 50mm, disc-shaped test plate with a thickness of 3mm. Using this plate, the b value was measured according to JIS K7105. The smaller the b value, the weaker the yellow tone and the better the hue. The measurement of the formed plate used a spectroscopic color difference meter SE2000 manufactured by Nippon Denshoku Kogyo Co., Ltd. 7) Amount of vinyl terminal groups: The measurement of ¹ H-NMR was carried out under the following conditions. ･ ¹ H-NMR measurement conditions Device: Bruker AVANZE III HD 500MHz Flip angle (flip angle): 30 degrees Waiting time: 1 second Accumulated times: 500 Measurement temperature: room temperature (298K) Concentration: 5wt% Solvent: inside heavy chloroform Standard substance: Tetramethylsilane (TMS) 0.05wt% 8) Amount of residual phenol and residual diphenyl carbonate (DPC): 1.0g of polycarbonate resin weighed by a precision scale, dissolved in 10ml of dichloromethane, stirring while Slowly add to 100ml of methanol to reprecipitate the resin. After sufficient stirring, the precipitate was filtered off, the filtrate was concentrated by an evaporator, the obtained solid was precisely weighed, and 1.0 g of a standard substance solution was added. Furthermore, 1 g of chloroform was added, and the diluted solution was quantified by GC-MS. Standard substance solution: 200ppm, chloroform solution of 2,4,6-trimethylphenol Determination device (GC-MS): Agilent HP6890/5973MSD Column: Capillary column DB-5MS, 30m×0.25mm ID, film thickness 0.5 μm Heating conditions: 50°C (5min hold) ~ 300°C (15min hold), 10°C/min Injection temperature: 300°C, injection volume: 1.0μl (split ratio 25) Ionization method: EI method Carrier gas: He , 1.0ml/min Aux temperature: 300°C Mass scanning range: 33-700 9) Amount of residual BHEBN and residual BPPEF: Dissolve 0.5g of weighed polycarbonate resin in 50ml of tetrahydrofuran (THF) as a sample solution. As a standard, a calibration line was prepared from the pure product of each compound, and 2 μL of the sample solution was quantified by LC-MS under the following measurement conditions. Furthermore, the detection limit value under this measurement condition is 0.01 ppm. LC-MS determination conditions: Determination device (LC part): Agilent Infinity 1260 LC System Column: ZORBAX Eclipse XDB-18, and guard cartridge Mobile phase: A: 0.01mol/L-ammonium acetate aqueous solution B: 0.01 mol/L-ammonium acetate in methanol solution C: THF Gradient program for mobile phase:

Flow rate: 0.3ml/column temperature: 45°C Detector: UV (225nm) Measuring device (MS part): Agilent 6120 single quad LCMS System Ionization source: ESI Polarity: Positive Fragmentation voltage: 100V Dry gas: 10L/min 、350℃ Nebulizer: 50psi Capillary voltage: 3000V Determination of ions: BHEBN: ion species=[M+NH ⁴ ] ^- , m/z=392.1 BPPEF: ion species=[M+NH ⁴ ] ^- , m/z=608.3 10 ) Formability: In the measurement of the b value above, the formability was evaluated based on the following criteria at the time of molding. A: The molded sheet has no voids and no waviness on the surface. B: The molded sheet has voids. C: The surface of the molded sheet has undulations. D: The molded sheet has voids and deformation on the surface. 11) PCT (Pressure Cooker Test): The injection molded product with a diameter of 50mm and a thickness of 3mm was kept at 120°C, 0.2Mpa, 100%RH, and 20 hours with PC-305SIII manufactured by HIRAYAMA Corporation, and then the sample was taken out and used in Japan. Denshoku Industry Co., Ltd. SE2000 spectroscopic colorimeter, measured by the method of JIS-K-7361-1.

[Manufacture of polycarbonate resin] (Example 1) As a raw material, 9,9-bis[6-(2-hydroxyethoxy)naphthalene-2-yl] fennel (hereinafter referred to as "BNEF") 18.85g (0.035 mol), 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene (hereinafter referred to as "BHEBN") 18.35g (0.049 mol), 9, 9-bis[4-(2-hydroxyethoxy)phenyl] fennel (hereinafter referred to as "BPEF") 7.02g (0.016 mol), diphenyl carbonate (hereinafter referred to as "DPC") 21.70g (0.101 mol), and 2.5×10 ^-2 mol/liter of sodium bicarbonate aqueous solution 32μl (8.0×10 ^-7 mol, which is 8.0× 10 ^-6 moles) into a 300ml four-neck flask with a stirrer and a distillation device, and heated to 180°C under a nitrogen environment of 760mmHg. After confirming that the raw materials were completely dissolved 10 minutes after the start of heating, stirring was performed for 110 minutes under the same conditions. Thereafter, while adjusting the degree of reduced pressure to 200 mmHg, the temperature was raised to 200° C. at a rate of 60° C./hr. At this time, it was confirmed that by-produced phenol started to distill off. Thereafter, the reaction was carried out by maintaining at 200° C. for 20 minutes. Furthermore, the temperature was raised to 230° C. at a rate of 75° C./hr, and 10 minutes after the end of the temperature rise, the temperature was maintained and the decompression degree was reduced to 1 mmHg or less for 1 hour. Thereafter, the temperature was raised to 245° C. at a rate of 60° C./hr, and stirring was further performed for 30 minutes. After the reaction, nitrogen was introduced into the reactor, the pressure was returned to normal pressure, and the produced polycarbonate resin was taken out.

Table 2 shows the physical property values of the obtained resin. Also, after confirming the ratio of the H ¹ -NMR spectrum of the resin, it is (peak integral value of 4.75-4.69ppm)/(peak integral value of 4.85-2.80ppm)×100=0.029, (peak integral value of 4.59-4.55ppm value)/(4.85～2.80ppm peak integral value)×100=not detected, (3.62～3.26ppm peak peak integral value)/(4.85～2.80ppm peak peak integral value)×100=0.189, (4.83～4.76 The peak integral value of ppm)/(the peak integral value of 4.85～2.80ppm)×100=0.026, the b value is 4.1, the residual phenol content in the resin is 300 ppm, and the residual DPC content is 50 ppm. The obtained NMR chart is shown in FIG. 1 .

(Example 2) As raw materials, 17.77 g (0.033 moles) of BNEF, 18.72 g (0.050 moles) of BHEBN, 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl 10.04g (0.017 mol) of ] fennel (hereinafter referred to as "BPPEF"), 21.70g (0.101 mol) of DPC, and 32μl (8.0×10 ^-2 mol/liter) ^of sodium bicarbonate aqueous solution ⁷ moles, that is, 8.0×10 ⁻⁶ moles relative to a total of 1 mole of dihydroxy compounds), the same operation as in Example 1 was carried out.

Table 2 shows the physical property values of the obtained resin. Also, after confirming the ratio of the H ¹ -NMR spectrum of the resin, it is (peak integral value of 4.75 to 4.69 ppm)/(peak integral value of 4.85 to 2.80 ppm)×100=not detected, (4.59 to 4.55 ppm Peak integral value)/(peak integral value of 4.85～2.80ppm)×100=0.068, (peak integral value of 3.62～3.26ppm)/(peak integral value of 4.85～2.80ppm)×100=0.184, (4.83～4.76 The peak integral value of ppm)/(the peak integral value of 4.85～2.80ppm)×100=0.022, the b value is 4.2, the residual phenol content in the resin is 300 ppm, and the residual DPC content is 50 ppm. The obtained NMR chart is shown in FIG. 2 .

(Example 3) As raw materials, BNEF8.08g (0.015 mol), BPPEF 50.21g (0.085 mol), DPC21.70g (0.101 mol), and 2.5×10 ^-2 mol/liter of sodium bicarbonate were used The same operation as in Example 1 was carried out except that the aqueous solution was 32 μl (8.0×10 ^-7 mol, that is, 8.0×10 ^-6 mol relative to 1 mol of the total dihydroxy compound). Table 2 shows the physical property values of the obtained resin.

(Example 4) As raw materials, BNEF 29.62g (0.055 mol), BPPEF 26.58g (0.045 mol), DPC 21.70g (0.101 mol), and 2.5×10 ^-2 mol/liter of sodium bicarbonate were used The same operation as in Example 1 was carried out except that the aqueous solution was 32 μl (8.0×10 ^-7 mol, that is, 8.0×10 ^-6 mol relative to 1 mol of the total dihydroxy compound). Table 2 shows the physical property values of the obtained resin.

(Example 5) As raw materials, 40.40g (0.075 moles) of BNEF, 14.77g (0.025 moles) of BPPEF, 21.70g (0.101 moles) of DPC, and 2.5×10 ^-2 moles/liter of sodium bicarbonate were used The same operation as in Example 1 was carried out except that the aqueous solution was 32 μl (8.0×10 ^-7 mol, that is, 8.0×10 ^-6 mol relative to 1 mol of the total dihydroxy compound). Table 2 shows the physical property values of the obtained resin.

(Example 6) As raw materials, BNEF8.08g (0.015 mol), BHEBN18.72g (0.050 mol), BPEF 15.35g (0.035 mol), DPC21.70g (0.101 mol), and 2.5×10 ^- 32 μl of ² mol/liter sodium bicarbonate aqueous solution (8.0×10 ^-7 mol, that is, 8.0×10 ^-6 mol relative to the total 1 mol of the dihydroxy compound), other than that Same operation as in Example 1. Table 2 shows the physical property values of the obtained resin.

(Example 7) As raw materials, BNEF29.62g (0.055 mol), BHEBN13.11g (0.035 mol), BPEF 4.39g (0.010 mol), DPC21.70g (0.101 mol), and 2.5×10 ^- 32 μl of ² mol/liter sodium bicarbonate aqueous solution (8.0×10 ^-7 mol, that is, 8.0×10 ^-6 mol relative to the total 1 mol of the dihydroxy compound), other than that Same operation as in Example 1. Table 2 shows the physical property values of the obtained resin.

(Example 8) As raw materials, BNEF40.40g (0.075 mol), BHEBN7.49g (0.020 mol), BPEF2.19g (0.005 mol), DPC21.70g (0.101 mol), and 2.5×10 ^- 32 μl of ² mol/liter sodium bicarbonate aqueous solution (8.0×10 ^-7 mol, that is, 8.0×10 ^-6 mol relative to the total 1 mol of the dihydroxy compound), other than that Same operation as in Example 1. Table 2 shows the physical property values of the obtained resin.

(Example 9) As raw materials, BNEF8.08g (0.015 mol), BHEBN16.85g (0.045 mol), BPPEF23.63g (0.040 mol), DPC21.70g (0.101 mol), and 2.5×10 ^- 32 μl of ² mol/liter sodium bicarbonate aqueous solution (8.0×10 ^-7 mol, that is, 8.0×10 ^-6 mol relative to the total 1 mol of the dihydroxy compound), other than that Same operation as in Example 1. Table 2 shows the physical property values of the obtained resin.

(Example 10) As raw materials, BNEF29.62g (0.055 mol), BHEBN14.98g (0.040 mol), BPPEF2.95g (0.005 mol), DPC21.70g (0.101 mol), and 2.5×10 ^- 32 μl of ² mol/liter sodium bicarbonate aqueous solution (8.0×10 ^-7 mol, that is, 8.0×10 ^-6 mol relative to the total 1 mol of dihydroxy compounds), other than that Same operation as in Example 1. Table 2 shows the physical property values of the obtained resin.

(Example 11) As raw materials, BNEF40.40g (0.075 mol), BHEBN7.49g (0.020 mol), BPPEF2.95g (0.005 mol), DPC21.70g (0.101 mol), and 2.5×10 ^- 32 μl of ² mol/liter sodium bicarbonate aqueous solution (8.0×10 ^-7 mol, that is, 8.0×10 ^-6 mol relative to the total 1 mol of dihydroxy compounds), other than that Same operation as in Example 1. Table 2 shows the physical property values of the obtained resin.

(Example 12) As a raw material, BNEF10.77g (0.020 mole) and BHEBN29.95g (0.080 mole) were used, and the operation similar to Example 1 was performed except not using BPEF. Table 2 shows the physical property values of the obtained resin.

(Example 13) As raw materials, use BNEF18.64g (0.035 moles), BHEBN23.70g (0.063 moles), DPC21.30g (0.099 moles), and 2.5× ^10-2 moles/liter of sodium bicarbonate The same operation as in Example 12 was performed except that the aqueous solution was 32 μl (8.0×10 ^-7 mol, that is, 8.1×10 ^-6 mol relative to 1 mol of the total dihydroxy compounds). Table 2 shows the physical property values of the obtained resin.

(Example 14) As raw materials, 29.28g (0.054 moles) of BNEF, 16.41g (0.044 moles) of BHEBN, 21.30g (0.099 moles) of DPC, and 2.5×10 ^-2 moles/liter of sodium bicarbonate were used The same operation as in Example 1 was performed except that the aqueous solution was 32 μl (8.0×10 ^-7 mol, that is, 8.1×10 ^-6 mol relative to 1 mol of the total dihydroxy compounds). Table 2 shows the physical property values of the obtained resin. Also, after confirming the ratio of the H ¹ -NMR spectrum of the resin, it is (peak integral value of 4.75 to 4.69 ppm)/(peak integral value of 4.85 to 2.80 ppm)×100=not detected, (4.59 to 4.55 ppm Peak integral value)/(peak integral value of 4.85～2.80ppm)×100=not detected, (peak integral value of 3.62～3.26ppm)/(peak integral value of 4.85～2.80ppm)×100=0.4925, (4.83 ～4.76ppm peak integral value)/(4.85～2.80ppm peak integral value)×100=0.023. The obtained NMR chart is shown in FIG. 3 .

(Example 15) As raw materials, use BNEF40.00g (0.074 mol), BHEBN9.12g (0.024 mol), DPC21.40g (0.100 mol), and 2.5× ^10-2 mol/liter of sodium bicarbonate The same operation as in Example 1 was performed except that the aqueous solution was 32 μl (8.0×10 ^-7 mol, that is, 8.1×10 ^-6 mol relative to 1 mol of the total dihydroxy compounds). Table 2 shows the physical property values of the obtained resin.

(Example 16) As raw materials, BNEF8.0kg (14.85 moles), BHEBN7.5kg (20.03 moles), BPPEF7.5kg (12.70 moles), DPC10.5kg (49.02 moles), and 2.5×10 ^- 16 ml (4.0×10 ^-4 mol, 8.4×10 ^-6 mol relative to the total 1 mol of dihydroxy compound) of ² mol/liter sodium bicarbonate aqueous solution was placed in the attached mixer and In the 50L reactor of the distillation unit, under a nitrogen environment of 760mmHg, heat to 180°C. After confirming that the raw materials were completely dissolved 30 minutes after the start of heating, stirring was performed for 120 minutes under the same conditions. Thereafter, while adjusting the degree of reduced pressure to 200 mmHg, the temperature was raised to 200° C. at a rate of 60° C./hr. At this time, it was confirmed that by-produced phenol started to distill off. Thereafter, the reaction was carried out by maintaining at 200° C. for 20 minutes. Furthermore, the temperature was raised to 230° C. at a rate of 75° C./hr, and 10 minutes after the completion of the temperature rise, the temperature was maintained and the decompression degree was reduced to 1 mmHg or less over 2 hours. Thereafter, the temperature was raised to 245° C. at a rate of 60° C./hr, and stirring was further performed for 40 minutes. After the reaction is finished, nitrogen is introduced into the reactor, the pressure is returned to normal pressure, and the produced polycarbonate resin is granulated and taken out. The b value of the obtained resin was 4.2, the residual phenol content in the resin was 100 ppm, the residual DPC content was 50 ppm, the residual BHEBN content was 20 ppm, and the residual BPPEF content was 5 ppm.

(Example 17) As raw materials, BNEF6.9kg (12.81 moles), BHEBN9.3kg (24.84 moles), BPPEF5.9kg (9.99 moles), DPC10.5kg (49.02 moles), and 2.5×10 ^- 16 ml of ² mol/liter sodium bicarbonate aqueous solution (4.0×10 ^-4 mol, that is, 8.4×10 ^-6 mol relative to the total 1 mol of dihydroxy compounds), otherwise The same operation as in Example 16 was carried out, and the resulting polycarbonate resin pellets were taken out. The b value of the obtained resin was 2.7, the residual phenol content in the resin was 200 ppm, the residual DPC content was 160 ppm, the residual BHEBN content was 15 ppm, and the residual BPPEF content was 5 ppm.

(Comparative Example 1) As raw materials, 28.05g (0.075 moles) of BHEBN, 10.96g (0.025 moles) of BPEF, 1.70g (0.101 moles) of DPC, and 2.5×10 ^-2 moles/liter of sodium bicarbonate were used The same operation as in Example 1 was carried out except that the aqueous solution was 32 μl (8.0×10 ^-7 mol, that is, 8.0×10 ^-6 mol relative to 1 mol of the total dihydroxy compound).

Table 2 shows the physical property values of the obtained resin. Also, after confirming the ratio of the H ¹ -NMR spectrum of the resin, it is (peak integral value of 4.75-4.69ppm)/(peak integral value of 4.85-2.80ppm)×100=1.013, (peak integral value of 4.59-4.55ppm value)/(4.85～2.80ppm peak integral value)×100=not detected, (3.62～3.26ppm peak peak integral value)/(4.85～2.80ppm peak peak integral value)×100=1.615, (4.83～4.76 Integral value of peak in ppm)/(Integral value of peak in 4.85～2.80ppm)×100=Not detected, b value is 5.3.

(Comparative Example 2) As raw materials, use BHEBN28.05g (0.075 mol), BPPEF14.77g (0.025 mol), DPC21.70g (0.101 mol), and 2.5× ^10-2 mol/liter of sodium bicarbonate The same operation as in Example 1 was carried out except that the aqueous solution was 32 μl (8.0×10 ^-7 mol, that is, 8.0×10 ^-6 mol relative to 1 mol of the total dihydroxy compound).

Table 2 shows the physical property values of the obtained resin. Also, after confirming the ratio of the H ¹ -NMR spectrum of the resin, it is (peak integral value of 4.75 to 4.69 ppm)/(peak integral value of 4.85 to 2.80 ppm)×100=not detected, (4.59 to 4.55 ppm Peak integral value)/(4.85～2.80ppm peak integral value)×100=1.120,0.021,(3.62～3.26ppm peak peak integral value)/(4.85～2.80ppm peak peak integral value)×100=1.570,(4.83 ～4.76 ppm peak integral value)/(4.85～2.80ppm peak integral value)×100=not detected, b value is 6.0.

(Comparative Example 3) As raw materials, BPEF5.6kg (12.81 moles), BHEBN9.3kg (24.84 moles), BPPEF5.9kg (9.99 moles), DPC10.5kg (49.02 moles), and 2.5×10 ⁻ 16 ml of ² mol/liter sodium bicarbonate aqueous solution (4.0×10 ^-4 mol, that is, 8.4×10 ^-6 mol relative to the total 1 mol of dihydroxy compounds), otherwise The same operation as in Example 16 was carried out, and the resulting polycarbonate resin pellets were taken out. The b value of the obtained resin was 4.1. Table 2 shows the physical property values of the obtained resin.

[ Fig. 1 ] H ¹ -NMR chart of the resin produced in Example 1. [ Fig. 2 ] H ¹ -NMR chart of the resin produced in Example 2. [ Fig. 3 ] H ¹ -NMR chart of the resin produced in Example 14.

Claims (10)

A monomer composition mainly composed of a compound represented by the following general formula (4), which contains a compound represented by the following formula (B), and/or any one of a and b in the compound of the general formula (4) Compounds that are 0;

(In the general formula (4), X represents an alkylene group with 1 to 4 carbon atoms, and a and b each independently represent an integer of 1 to 10);

(In the formula (B), X represents an alkylene group having 1 to 4 carbon atoms, a and b each independently represent an integer of 1 to 10, and Hm is a hydrogen atom, respectively). Such as the monomer composition of claim 1, which contains a compound in which any one of a and b is 0 in the compound of the general formula (4), and its content is higher than that of the compound with the compound of the general formula (4) as the main component. In the body composition, it is 1000ppm or less. The monomer composition according to claim 1, which contains terfenone, and its content is 1000ppm or less in the monomer composition containing the compound of general formula (4) as the main component. Such as the monomer composition of claim 1, which is a monomer of polycarbonate. The monomer composition as claimed in item 1, wherein the compound of the aforementioned general formula (4) is 9,9-bis[6-(2-hydroxyethoxy)naphthalene-2-yl]terylene. A method for producing polycarbonate resin, comprising A step of melt polycondensation of the monomer composition according to claim 1 and the carbonic acid diester. The method according to claim 6, which comprises using a transesterification catalyst selected from alkali metal compounds, alkaline earth metal compounds and nitrogen-containing compounds to carry out melt polycondensation. As the method of claim item 7, wherein the aforementioned transesterification catalyst is selected from sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, acetic acid Sodium, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenyl borate, sodium benzoate, potassium benzoate, benzoin Cesium phosphate, lithium benzoate, 2 sodium hydrogen phosphate, 2 potassium hydrogen phosphate, 2 lithium hydrogen phosphate, 2 sodium phenyl phosphate, 2 sodium salt of bisphenol A, 2 potassium salt, 2 cesium salt or 2 lithium salt, phenol Sodium, potassium, cesium or lithium salts and combinations thereof. The method according to claim 7 or 8, wherein the transesterification catalyst is used at a ratio of 1×10 ^-7 to 1×10 ^-4 mol relative to 1 mol of the total dihydroxy compound. The method according to any one of claims 6 to 9, wherein the aforementioned melt polycondensation is carried out at a temperature of 180 to 245°C.

Images